EP0693877A1

EP0693877A1 - USE OF 7-ETHYNYL $g(a)-(METHOXYMETHYLENE) 1-NAPHTHALENE ACETIC ACID DERIVATIVES FOR PREPARING FUNGICIDAL COMPOSITIONS

Info

Publication number: EP0693877A1
Application number: EP94913645A
Authority: EP
Inventors: Peter Braun; Burkhard Sachse
Original assignee: Roussel Uclaf SA
Current assignee: Sanofi Aventis France
Priority date: 1993-04-15
Filing date: 1994-04-14
Publication date: 1996-01-31
Also published as: WO1994023576A1; JPH08508987A; CA2160577A1; FR2703880B1; FR2703880A1

Abstract

The use of compounds of formula (I), wherein R is H, halogen, or straight, branched or cyclic alkyl optionally interrupted by one or more O, S or N, or R is aryl, aryloxy, optionally substituted heterocyclic aryl, or ( alpha ), wherein p = 0-6, or R is ( beta ) wherein Ra, Rb and Rc are alkyl, or R is ( psi ), wherein a and b are H, halogen, OH, alkyl, alkoxy or a and b together form a cycloalkyl, and R2, R3 are H, alkyl or ( delta ), for producing fungicidal compositions, is disclosed.

Description

Use of derivatives of 7-ethynyl α-fmethoxy methylene acid. 1-acetic naphthalene for the preparation of fungicidal compositions.

The present invention relates to the use of derivatives of acid 7-ethynyl α- (methoxymethylene) 1-naphthalene acéti¬ that for the preparation of fungicidal compositions.

The subject of the invention is the use of the compounds of formula (I):

in which R represents:

- a hydrogen or halogen atom, - an alkyl radical containing up to 8 linear, branched or cyclic saturated or unsaturated carbon atoms, optionally substituted by one or more hydroxyl radicals, by one or more atoms of halogen, optionally interrupted by one or more heteroatoms chosen from oxygen, nitrogen or sulfur atoms,

- a radical - (CH ₂ ) _p in which p represents an integer equal to 0, 1, 2, 3, 4, 5 or 6, and R ' ₁ and R' ₂ identical or different represent a hydrogen atom, a linear or branched alkyl radical, containing up to 4 carbon atoms, - an aryl or aryloxy radical containing up to 18 carbon atoms optionally substituted on the aryl ring by one- or more substituents chosen from halogen atoms, the radical N0 ₂ , the radical C≡N, the alkyl, O-alkyl and S-alkyl radicals, linear, branched or cyclic, saturated or unsaturated, containing up to 8 carbon atoms, optionally substituted by one or more halogen atoms, the aryl or aryloxy radicals containing up to 16 carbon atoms, optionally substituted by one or more halogen atoms and the radical

in which R "- ^ and R", identical or different from each other, represent a hydrogen atom, an alkyl radical containing up to 4 carbon atoms or an aryl radical containing up to 18 atoms carbon, optionally substituted by one or more halogen atoms,

an aryl or aryloxy radical containing up to 18 carbon atoms optionally substituted on two adjacent carbon atoms of the aryl ring by a methylene or ethylenedioxy group optionally substituted by one or two halogen atoms,

a heterocyclic 5 or 6-membered aryl radical containing 1, 2 or 3 heteroatoms chosen from oxygen, sulfur and nitrogen atoms, optionally substituted by one or more radicals chosen from the group consisting of hydroxyl radicals, N0 ₂ , C≡N, halogen atoms, alkyl, O-alkyl and S-alkyl radicals, containing up to 8 carbon atoms, linear, branched or cyclic optionally substituted by one or more halogen atoms, by one or more hydroxyl radicals and the radicals

-could

<pu /

^R 2 in which R "^ and R '" _{2, which are} identical or different, represent a hydrogen atom or an alkyl radical containing up to 4 carbon atoms,

Ra

- an Si -—Rb radical

\ Rc in which Ra, Rb and Rc, identical or different, represent a linear, branched or cyclic alkyl radical containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms, an aryl radical optionally substituted by one or more halogen atoms, one or more hydroxyl radicals, one or more alkyl radicals, linear or branched, optionally substituted by one or more halogen atoms, 'one or more O-alkyl or S radicals -alkyl containing up to 8 carbon atoms, optionally substituted by one or more halogen atoms, ab \ / or R represents a radical -CR 'in which a and b, identical or different, represent a hydrogen atom, a halogen atom, a hydroxyl radical, a linear or branched alkyl radical containing up to 6 carbon atoms optionally substituted by one or more halogen atoms or a linear or branched alkoxy radical containing up to 6 atoms carbon, or a and b together with the carbon atom to which they are linked form a cycloalkyl radical containing up to 6 carbon atoms, and R 'represents one of the values indicated above for R, ab to the exception of the value -C-R ', R ₂ and R ₃ identical or different from each other represent an alkyl radical containing up to 8 carbon atoms, linear, branched or cyclic, optionally substituted by one or more

halogen atoms, or by a radical, in which Ra, Rb and Rc have the meanings indicated above, for the manufacture of fungicidal compositions.

In the definition of the various substituents: - alkyl preferably represents a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl radical,

- cycloalkyl preferably represents cyclopropyl, cyclobutyl, cyclopentyl, - unsaturated alkyl preferably represents ethenyl, ethyl, propenyl, propynyl, butenyl, butynyl,

- when the linear or branched alkyl radical is interrupted by one or more heteroato es, it is a question of preferably one or more oxygen or nitrogen atoms,

when it is a cycloalkyl radical interrupted by one or more heteroatoms, it is preferably a nitrogen heterocycle linked by a nitrogen atom such as pyrrolidine, pyrazoline, piperidine, piperazine or orpholine,

- aryl preferably represents the phenyl radical,

heterocyclic aryl preferably represents a thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl (1,2,4) or (1,3,4), triazolyl, imidazolyl, pyridynyl, pyrimidynyl or pyrazolyl radical,

- if R or R 'represents a halogen, it is preferably a bromine or chlorine atom,

- If R or R 'represents a radical itself substituted by a halogen atom, the halogen is preferably a fluorine, chlorine or bromine atom.

The invention more particularly relates to the use of the compounds of formula (I) in which the radical R ₂ represents a methyl radical as well as the use of those in which R ₃ represents a methyl radical, for the manufacture of fungicidal compositions.

The geometry of the exo double bond (enol ether) is E or Z and the invention which relates to the use of the products E and of the products Z, as well as mixtures E + Z, has more specifically for object l use of the compounds in which the geometry of the exo double bond (enol ether) is E. Among the preferred uses of the invention, mention may be made of the use of the compounds of formula (I) in which R represents a radical alkyl containing up to 6 carbon atoms and very particularly the use of the compounds of formula (I) in which R represents an isopropyl radical, as well as those in which R represents a terbutyl radical, mention may also be made of the use of compounds of formula (I) in which R represents an ab -CR 'radical in which a and b which are identical or different represent a hydrogen atom, a hydroxyl radical, a linear or branched alkyl radical containing up to 4 atoms carbon or a and b form together with the atom of carbon to which they are linked a cycloalkyl radical containing up to 4 carbon atoms and R 'has the significance indicated above and in particular the use of compounds of formula (I) in which R represents a radical:

CH ₃

for the manufacture of fungicidal compositions or the use of those in which R represents a radical

or the use of those in which R represents a hydrogen atom, a phenyl radical, a trimethyl silyl radical or a pyridinyl radical. The invention particularly relates to the use of the compounds of formula (I), the preparation of which is set out below and very particularly the compounds of preparations 1, 7 and 10 or even that of the compounds of preparations 2, 4 , 5, 8, 13 and 24 for the manufacture of fungicidal compositions.

A more particular subject of the invention is the use of the compounds of formula (I) as defined above for the manufacture of fungicidal compositions containing from 0.001 to 1% by weight of compounds of formula (I). The compounds of formula (I) exhibit excellent fungicidal activity. They make it possible to fight against the mushrooms which have already penetrated inside the plant tissues. Which is particularly interesting in the case where it is no longer possible to control diseases caused by fungi once contamination has already occurred. The activity spectrum of the compounds of formula (I) covers a large number of phytopathogenic fungi of various economic importance, for example Pyricularia cryzae, Venturia inaequalis, Cercospora beticola, Erysiphica- ceae (Sp. Powdery mildew), Fusarium- , Drechslera- and Leptosphaeria-, Plasmopara viticola, Phytophtora infestans, Pseudoperonospora cubensis, various rusts, strains of Botrylis cinerea sensitive and resistant to BCM- and / or Dicarboximide-, Sclerotinia solerotioru, strains of Pseudocercosporella herpotrich Pellicularia sasakii.

In addition, the compounds of the invention can also be used in different industrial sectors, for example to protect wood or as a preservative for paints.

The invention also extends to compositions which contain, in addition to the compounds of formula (I), suitable formulating agents and the invention particularly relates to fungicidal compositions containing from 0.001 to 1% by weight of compounds of formula ( I).

The possible formulations vary according to biological and physicochemical parameters. They can be, for example, wettable powders, emulsifiable concentrates, aqueous solutions, emulsions, spray solutions, dispersions in oil or in water, suspoemulsions, powders, treatment of seeds, of granules for example of microgranules, of granules to be sprayed, of granules coated, of absorption granules, of granules dispersible in water, of ULV formulation, of microcapsules, of waxes or of baits.

These types of formulations are known and are described for example by Winnacker-Kϋchler, "Chemische Technologie (Chemical Technology)", Volume 7, C-Hauser Verlag, Munich, 4th Ed., 1986; van Falkenburg, "Pesticides Formulations", by Marcel Dekker NY, 2nd Ed. 1972-73 or by K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.

The various suitable formulating agents, such as inert materials, surfactants, solvents and other additives are known and described for example by Watkins, "Handbook of Insecticide Dust Diluents and

Carriers ", 2nd Ed. Darland Book, Caldwell N.J., by H.v. Olphen," Introduction to Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, N.Y.; by Marschen, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; by Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964, by Schδnfeldt, "Grenzflàchenaktive Athylenoxidaddukte (Surfaceactive Ethylene Oxide Adducts)", Wiss. Verlagsgesell. , Stuttgart 1976; or by Winnacker-Kϋchler, "Chemische Technologie (Chemical Technology)", Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986.

Combinations with other active ingredients such as pesticides, fertilizers and / or growth regulators can be prepared on the basis of these formulations, it can be a ready-to-use mixture or a tank mixture .

Wettable powders are preparations which can be dispersed uniformly in water and contain, in addition to the active substance, other wetting agents, such as polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkylsulfonates or alkylphenosulfonates and dispersing agents. such as sodium ligninsulfonate, 2,2'-dinaphthylmethane, 6,6'-sodium disulfonate, sodium dibutylnaphthalene sulfonate, or sodium oleimethyltaurinate, with a further diluting or inert agent. To prepare emulsifiable concentrates, the active ingredient is dissolved with an organic solvent such as methanol, butanol, cyclohexanone, dimethylformamide, xylene, or other aromatic compounds or other boiling point hydrocarbons more high with additionally one or more emulsifying agents. As examples of emulsifying agents, mention may be made of calcium salts of arylalkylsulfonic acid, such as calcium dodecylbenzenesulfonate, or non-ionic emulsifiers such as fatty acid polyglycol esters, alkylarylpolyglycol ethers, polyglycol ethers, fatty acid esters of propylene oxide and ethylene oxide , polyoxyethylene fatty acid esters, or polyoxyethylene esters.

To obtain powders, the active ingredient can be ground with finely divided substances such as talc or natural clays such as kaolin, bentonite, pyrophylite or diatomaceous earth. To obtain granules, it is possible to spray the active material on granules of inert adsorbent material or to apply concentrates of active material to the surface of vehicles such as sand, kaolin or granules of active material by means of ligands such as polyvinyl alcohols, sodium polyacrylates, or mineral oils. One can thus make granules of active ingredient in a conventional manner for fertilizers, by mixing, if desired, the active substance with fertilizers. In the case of wettable powders, the concentration of active principle is for example from 10 to 90% by weight, the remainder being constituted by conventional ingredients of formulation. In the case of emulsifiable concentrates, the concentration of active principle is approximately 5 to 80% by weight. The formulations in powder form usually contain from 5 to 20% by weight of active principle, the solutions for spray from 2 to 20% by weight approximately. In the case of granules, the concentration of active principle varies according to whether the active principle is liquid or solid and according to the auxiliary substances of formulation used.

In addition, the compositions optionally contain adhesives, wetting agents, dispersants, emulsifiers, penetrating agents, solvents, fillers and vehicles. For use, commercially available concentrates are usually diluted with water in the case of wettable powders, emulsifiable concentrates, dispersants and sometimes microgranules. The preparations in the form of powders or granules and the solutions for sprays are generally not diluted with other substances before use.

The amount of active ingredient to be applied varies with external conditions such as temperature and humidity. It can vary within wide limits, for example between 0.005 and 10.0 kg / ha or more, but preferably from 0.01 to 5 kg / ha.

The compounds of formula (I) can be used either alone or in combination with other fungicides.

Examples of fungicides which can be used include the following products:

Anilazine, Benalaxyl, Benodanil, Benomyl, Binapacryl, Biteranol, Buthiobat, Captafol, Captan, Carbendazim, Carboxin, Chlobenzthiazone, Chlorthalonil, copper compounds such as copper oxychloride, copper oxide, Cymoxannil, Cyproconanole, Cyproconazole, Dichlomezine, Diclobutrazol, Diethofencarb, Difluconazole, Dimethirimol, Dimethomorph, Diniconazole, Dinocap, Dithianon, Dodemorph, Dodine, Edifenfos, Ethirimol, Etridiazol, Fenarimol,

Fenfuram, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentin-acetate, Fentinhydroxide, Fluaziram, Fluobenzimine, Fluorimide, Flusilazole, Flutolanil, Flutriafol, Folpet, Fosetylaluminium, Fuberidazole, Furalaxen, Iuralproxazon, Guimoxaz, Mancozeb, Maneb, Mepronil, Metalaxyl, Methasulfocarb, Methfuroxam, Myclobutanil, Nabam, Nitrothalisopropyl, Nuarimol, Ofurace, Oxadixyl, Oxycarboxin, Penconazol, Pencycuron, PP 969, Probenazole, Propenbocar, Prchlorac, Prchlorab, Prochlorab, Prochlorab, , Pyroquilon, Rabenzazole, Sulfide, Tebuconazole, Thiabendazole, Thiofanatemethyl, Thiram, Tololofos methyl sodium C13 / 15, Esters of sodium cetostearylphosphate, Sodium dioctylsulfosuccinate, Isopropylna phthalenesulfonate sodium, Sodium methylenapthalene sulfonate, Cetyltrimethylammonium chloride, salts of primary, secondary or tertiary long chain amines, alkylpropyleneamine, laurylpyrimidinium bromide, lipidamine quaternary ammonium ethylate, Alkylldiethyl ammonium chloride , and 1-hydroxyethyl 2-alkylimidazoline.

These are known products, most of which are described by CHR orthing US B. alker, The Pesticide Manual, 7th Ed. (1983) British Crop Protection. The compounds of the invention can also be formulated with other active ingredients, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth regulators or herbicides. As examples of insecticides, mention may be made of phosphoric esters, carbamates, carboxylic esters, forma idines, tin derivatives and substances prepared by fermentation.

As examples of phosphoric esters, there may be mentioned: Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Bromophos, Bromophos-ethyl, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-ethyl, Demeton, Demeton-S- methyl, Demeton-S -methyl sulphone, Dialifos, Diazinon, Dichlorvos, Dicrotophos, 0,0-1,2,2,2-tetrachlorethylphosphorothioate (SD 208 304), Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fena iphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos, For othion, Heptonophos, Isozophos, Isothioate, Isoxathion, Malathion, Methacrifos, Methamidophos, Methidation, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton

Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinphos, Pyridapenthion, Quinalphos, Quinphos, Thiometon, Triazophos, Trichlorphon, Vamidothion.

As examples of carbamates, there may be mentioned: Aldicarb, 2-sec-butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloathocarb, Benfuracarb, Ethiofen- carb, Furathiocarb, Isoprocarb, Methomyl, 5-methyl-m-cumenyl- butyryl (methyl) carbamate, Oxamyl, Pirimicarb, Propoxur, Thio- dicarb, Thifanos, 4,9 -triaza-4-benzyl-6,10-dimethyl- 8-oxa7-oxo-5, ll-dithia-9-dodecenoate (OK 135), 1-methylthio (ethylidene-amino) N-methyl N- (morpholinothio) carbamate (UC 51717).

As examples of carboxylic esters, mention may be made of: Allethrine, Alphametrine, 5-Benzyl 3-furylmethyl (E) - (1R) -cis 2,2-dimethyl 3- (2-oxothiolan 3-ylidenemethyl) cyclopropane-carboxylate, Biolallethrine , (S) Bioallethrine, Bioresmethrine, Biphenate, (RS) -l-cyano l- (6-phenoxy 2-pyridyl) methyl (1RS) trans-3- (4-tert-butylphenyl) 2,2-dimethylcyclopropanecarboxylate ( NCI 85193), Cycloprothrine, Cyhalothrine, Cypermethrine, Cyphenothrine, Deltamethrine, Empenthrine, Esfenvalerate, Fenfluthrine, Fenpropathrine, Fenvalerate, Flucythrinate, Flumethrine, Fluvalinate (D-isomer), Permethrine, Phenothrine (R-isomer), d -prethrin ), Res ethrine, Tefluthrine, Tetramethrine, Tralomethrine.

As examples of amidine, there may be mentioned: Amitraz, Chlordimeform.

Examples of tin compounds include: Cyhexatin and Fenbutatinoxide. We can also cite other products such as:

Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2- (4- (Chlorphenyl) 4,5-diphenylthiophene (UBI-T 930), Clofentezine, ester 2- methyl naphthyl methyl of cyclopropanecarboxylic acid, Cyromazine, ethyl ester of N- (3,5-dichlor 4- (1,1,2,3,3,3- hexafluor 1-propyloxy) phenyl) carbamoyl) 2 -chlorbenzcarboximidique, DDT, Dicofol, N- (N- (3,5-dichlor 4- (1,1,2,2-tetrafluoroethoxy) phenylamino) carbonyl) 2,6-difluorbenzamid, Diflubenzuron, N- ( 2,3-dihydro 3-methyl 1,3-thiazol 2-ylidene) 2,4-xylidine, Dinobuton, Dinocap, Endosulfan, Ethofenprox, (4-ethoxyphenyl) (di ethyl) (3- (3-phenoxyphenyl) propyl) silane, (4-ethoxyphenyl) (3- (4-fluoro 3-phenoxyphenyl) pro- pyl) dimethylsilane, Fenoxycarb, 2-fluoro 5- (4- (4-ethoxy- phenyl 4-methyl 1-pentyl) diphenylether, Fenthiocarb, Flubenzimine, Flucycloxuron, Flufenoxuron, Gamam-HCH, Hexythiazox, Hydramethylnon, Ivermectin, 2 -nitromethyl 4,5- dihydro 6H-thiazine, 2-nitromethyl 3,4-dihydrothiazol, 2- nitromethylene 1,2-thiazinan 3-ylcarbamaldehyde, Propargite, Teflubenzuron, Tetradifon, Tetrasul, Thiocyclam, Triflumuron. formulations used, prepared from commercially available formulations, vary within wide limits.The concentration of active principle in the form used varies from 0.0001 to 100% by weight of active principle, and preferably between 0.001 and 1% weight.

The following examples illustrate the invention without, however, limiting it.

EXAMPLES OF FORMULATIONS a) A powder is prepared by mixing 10 parts by weight of active material with 90 parts by weight of talc and mixing the whole in a mortar. b) A wettable powder easily dispersible in water is prepared by mixing 25 parts by weight of active material, 65 parts by weight of quartz containing koalin as inert material, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyl taurinate as a wetting and dispersing agent and by molding the mixture in a needle disc mill. c) A dispersion concentrate that is easily dispersible in water is prepared by mixing 40 parts by weight of active substance, 7 parts by weight of monoestersulfosuccinic, 2 parts by weight of sodium salt of ligninsulfonic acid, 51 parts by weight of water and molding the mixture to a shape less than 5 microns in a disc mill. d) An emulsifiable concentrate is prepared by mixing 15 parts by weight of active material, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of nonylphenol as emulsifier. e) Granules are prepared from 2 to 15 parts by weight of active material and from an inert carrier for granules like attapulgite, pumice granules and / or quartz sand. Advantageously, a suspen¬ sion of wettable powder of Example b is used, with a solid content of 30% which is vaporized on the surface of the granules. We dry and mix thoroughly. The proportion by weight of wettable powder is approximately 6% and that of the inert vehicle approximately 95% by weight of the finished granules. BIOLOGICAL EXAMPLES Study of the compounds of examples 1, 7, 10, 2, 4, 5, 8, 13 and 24 (hereinafter referred to as products A, B, C, D, E, F, G, H and I). EXAMPLE 1:

Field beans of the Herz Freya variety or 14-day Franck Ackers pearl are treated with an aqueous suspension of active principle until runoff. Once the product is dry, the plants are inoculated with a spore suspension (1.5 million spores / ml) of Botrytis cinerea. The plants are then left to develop in a controlled atmosphere chamber, at a temperature of 20 - 22 ° C and with a relative atmospheric humidity of 99%. Plant infection becomes apparent when black spots appear on leaves and stems. The reading is made one week after inoculation. The efficacy of the products is calculated relative to an untreated control. At the concentration of 500 ppm, products A, B, C, D, E, F, G, H and I have an efficiency of 100%. EXAMPLE 2:

Wheat of the Jubilar variety is treated at the "2 leaf" stage using an aqueous suspension of active principle until runoff. Once the product is dry, the plants are inoculated with an aqueous suspension of Puccinia recondita. The humid plants are placed in a controlled atmosphere chamber at 20 "C and under a relative humidity of 100% for 16 hours. The plants are then left to develop in a greenhouse at a temperature of 22 - 25 ° C and under a humidity relative atmospheric 50 ~ 70 I.

After a 2-week incubation, the fungi form spores on the entire surface of the control leaves, the extent of the disease can be assessed. The efficacy of the products is evaluated in relation to an untreated infested control.

At the concentration of 500 ppm, products A, B, C, D, E, F, G, H and I have an efficiency of 100%. EXAMPLE 3:

6 weeks after seeds, vine plants of the Riesling Ehrenfelder variety are treated with an aqueous suspension of active principle until renewal.

Once dry the product sprayed, the plants are inoculating them with a zoosporangia suspension of Plasmopara viticola and the wet plants are placed in a chamber at 23 ^° C and a relative atmospheric humidity of 80-90%.

After 7 days of incubation, the plants are placed in a culture chamber to promote the development of fungi. The extent of the disease is then assessed.

The degree of efficacy of the products is evaluated compared to an infested untreated control.

At the concentration of 500 ppm, products A, B, C, D, E, F, G, H and I have an efficiency of 100%. EXAMPLE 4:

Wheat of the Jubilar variety wheat is treated with an aqueous suspension of active ingredient, at the "2 leaf" stage until runoff. Once the product has vaporized dry, the plants are inoculated with an aqueous suspension of Leptosphaeris nodorum picnospores, and incubated for several hours in a room with controlled environment, at a relative atmospheric humidity of 100%. Plants are allowed to grow in a greenhouse at 90% relative atmospheric humidity until symptoms appear. The degree of effectiveness is expressed relative to an infested untreated control.

At the concentration of 500 ppm the compounds A, B, C, D, E, F, G, H and I have an efficiency of 100%. EXAMPLE 5 Barley plants of the Igri variety at the "2 leaf" stage are treated with an aqueous suspension of active principle until runoff.

Once the sprayed product is dry, the plants are inoculated -, _

an aqueous suspension of Pyrenophora teres spores and incubates for 16 hours in a room at 100% relative atmospheric humidity. The infested plants are then left to develop in the greenhouse at 25% at a relative humidity of 80%.

One week after inoculation the extent of the disease is assessed. The degree of efficacy of the products is evaluated compared to an infested untreated control.

At a concentration of 500 ppm of active ingredient, products A, B, C, D, E, F, G, H and I have an efficiency of 100%. EXAMPLE 6

Tomato plants of the Rheinlands Ruhn variety at stage 3, 4 leaves are treated uniformly with an aqueous suspension of active principle.

Once the product has vaporized dry, the plants are inoculated with a suspension of zoosporangia of Phytophtora infestans and kept in a culture chamber with optimal conditions of infection for 2 days. The plants are then left to grow in a greenhouse until symptoms appear.

The extent of the plant disease is assessed one week after inoculation. The degree of effectiveness of the products is evaluated relative to an untreated infected control. At the concentration of 500 ppm the compounds A, B, C, D, E, F, G, H and I have an efficiency of 100%. EXAMPLE 7:

Barley plants at the stage of "two leaves" are inoculated with powdery mildew conidia of barley (Erysiphe grasses p sp. Hordie) and placed in a greenhouse at 20 ^° C at a relative humidity of 50%, a day after inoculation. The plants are then treated with an aqueous suspension of active ingredient. We are looking for symptoms of powdery mildew. The degree of effectiveness is evaluated in relation to the untreated infested control. At the concentration of 500 ppm the compounds A, B, C, D, E, F, G, H and I have an efficiency of 100%. EXAMPLE 8:

Wheat plants of the Jubilar variety are treated with an aqueous suspension of active ingredient.

Once the product has vaporized dry, the stems are inoculated with an aqueous suspension of ycellium spores of Pseudocercosporella herpotrichoids, they are left to incubate for several days in a room with a relative humidity of 100%. The plants are allowed to develop in a greenhouse with a relative atmospheric humidity of 95% until the appearance of symptoms. The degree of effectiveness is evaluated in relation to the untreated controls. At a concentration of 500 ppm the compounds A, B, C, D, E, F, G, H and I have an efficiency of 100%.

The compounds of formula (I), described and claimed in European patent application No. 0 566 455 can be prepared according to a process characterized in that a compound of formula (II) is subjected:

in which Hal represents a halogen atom and R ₂ and R ₃ retain the same meaning as above with the action of a compound of formula (III):

RC≡CH (III)

in which R retains its previous meaning, to obtain the compound of formula (I), which is subjected, if desired and if R has a hydroxyl function, to a functionalizing agent to obtain the compound of formula (I) corresponding. In a preferred embodiment of the process, the reaction between the compound of formula (II) and the compound of formula (III) is carried out in an aprotic dipolar solvent such as acetonitrile, in the presence of a tertiary amine tertiary like triethylamine, metallic palladium supported by charcoal, a tertiary phosphine like triphenylphosphine and a copper-based catalyst like cuprous iodide. The compounds of formula (I) can also be prepared according to a process characterized in that a compound of formula (I) in which R represents a hydrogen atom is further subjected to the action of a compound of formula ArHal , in which Ar represents an optionally substituted aryl or heteroaryl radical and Hal represents a halogen atom to obtain the corresponding compound of formula (I) in which R represents an optionally substituted aryl or heteroaryl radical.

The compounds of formula (II) also described and claimed in European patent application No. 0 566 455 can be prepared from the compounds of formula (IV):

by the action of a strong base and an alkyl formate. The products of formula (IV) are described and claimed in European patent application No. 0 538 097.

The compounds of formula (I) in which R is a Ra group -Si Rb are biologically active products Rc and can also serve as intermediate products for preparing other biologically active products according to the following reaction schemes:

Ar-I

Ar

X

PR ₃

The compounds of formula (I), in which the radical R contains a hydroxyl function, can be functionalized using an alkylating reagent such as methyl iodide or dimethyl sulfate to yield the corresponding methoxy derivatives. They can also be subject to the action of the D.A.S.T. (dimethyl amino sulfide trifluoride) to lead to the derivatives in which R contains at least one fluorine atom.

The following preparation examples illustrate the processes for the preparation of compounds of formula (I) indicated above. PREPARATION 1: (E) 7- (3, 3-dimethyl 1-butynyl) α- (methoxy-methylene) l-naphthalene methyl acetate

1.5 g of (E) -7-bromo (α-methoxymethylene) l-naphthalene methyl acetate prepared as indicated in European patent application 0 566 455 are introduced into an anhydrous mixture of 15 cm ³ of triethylamine and 10 cm ³ of acetonitrile. 0.198 g of 10% palladium on activated carbon is added, 0.035 g of copper iodide, 0.195 g of triphenylphosphme and 0.60 cπr 3 of terbutylacetylene. The suspension obtained is brought to reflux for 5 hours, 1 cm ³ of terbu- is added. tylacetylene. It is again brought to reflux for 2 hours. It is filtered and brought to dryness. 2.62 g of a product are obtained which is chromatographed on silica eluting with a hexane-methylene chloride mixture (50-50). The fraction of rf = 0.20 is isolated, concentrated on a rotary evaporator, rinsed, dried at 50 ° C. 0.99 g of a product is obtained which is recrystallized from ethyl acetate. 0.630 g of sought product is thus obtained. Mp 172 ° C. δ (CDC1 ₃ ) = 7.79 ppm. By operating as above, the following products were obtained from the same product of formula (II) and the corresponding product RC≡CH.

* Melting points are expressed in degrees Celsius and are determined using a METTLER PF62 device. ** The chemical shifts (δ) are expressed in ppm from an internal reference tetramethylsilane and determined using a BRUCKER Nuclear Magnetic Resonance device at 250 MHz. PREPARATION 2: (E) o- (methoxymethylene) 7- [2- (trimethylsilyl) ethynyl] l-naphthalene methyl acetate F = 157 ^* C. δ (CDC1 ₃ ) = 7.79 ppm.

PREPARATION 3: (E) 7- (l-hexynyl) α- (methoxymethylene) l-naphthalene methyl acetate F = 88 ^* C. δ (CDC1 ₃ ) = 7.78 ppm. PREPARATION 4: (E) 7- [2- [1- (4-ethoxyphenyl) cyclopropyl] ethynyl] α- (methoxymethylene) l-naphthalene methyl acetate F = 145 "C. Δ (CDC1 ₃ ) = 7.78 ppm .

PREPARATION 5: (E) α- (methoxymethylene) 7- (phenylethynyl) l-naphthalene methyl acetate F = 161 ^* C. δ (CDC1 ₃ ) = 7.81 ppm.

PREPARATION 6: (E) 7- (3-hydroxy 3-methyl 1-butynyl) α-

(methoxymethylene) l-naphthalene methyl acetate

F = 117'C. δ (CDC1 ₃ ) = 7.80 ppm.

PREPARATION 7: (E) 7- (3-methoxy 3-methyl 1-butynyl) α- (methoxymethylene) l-naphthalene methyl acetate F = 134'C. δ (CDC1 ₃ ) ≈ 7.80 ppm.

PREPARATION 8: (E) 7- (3-hydroxy 3-phenyl 1-propynyl) o- (methoxymethylene) l-naphthalene methyl acetate F = 192 "C. Δ (CDC1 ₃ ) = 7.78 ppm.

PREPARATION 9: (E) 7- (3-hydroxy 3-phenyl l-butynyl) o- (methoxymethylene) l-naphthalene methyl acetate F = 169'C. δ (CDC1 ₃ ) = 7.79 ppm. PREPARATION 10: (E) 7- (3-methyl l-butynyl) α- (methoxymethy¬ lene) l-naphthalene methyl acetate F = 114 ^* C. (CDC1 ₃ ) = 7.78 ppm.

PREPARATION 11: (E) α- (methoxymethylene) 7- (cyclopentyl ethynyl) l-naphthalene methyl acetate F = 80 ^* C. δ (CDC1 ₃ ) = 7.78 ppm.

PREPARATION 12: (E) 7- (3-fluoro 3-methyl l-butynyl) α- (methoxymethylene) l-naphthalene methyl acetate

By reacting the product obtained in Preparation 6 with DAST (dimethyl a ino sulfide trifluoride) at -10 ° C in tetrahydrofuran, the desired product was obtained. F = 74'C. δ (CDC1 ₃ ) = 7.80 ppm.

PREPARATION 13: (E) α- (methoxymethylene) 7- (ethynyl) l-naphthalene methyl acetate

18.1 cm ³ of a solution of BU ₄ NF IN in THF are added at -50 ° C., in a solution containing 6.15 g of (E) α- (methoxymethylene) 7- [2- (trimethylsilyl ) ethynyl] l-naph¬ talene methyl acetate (prepared in preparation 2) and 180 cm ³ of THF. The reaction mixture is kept under agitation for 2 hours. It is poured onto an aqueous solution of potassium dihydrogen phosphate. Extraction is carried out with methylene chloride. Dried, the solvent evaporated and 6.1 g of a product is obtained which is chromatographed on silica eluting with a hexane-ethyl acetate mixture (9-1). 4.2 g of sought product is obtained. Mp 140 ° C. δ (CDC1 ₃ ) = 7.78 ppm. PREPARATION 14: (E) α- (methoxymethylene) 7- (bromoethynyl) l-naphthalene methyl acetate

3.5 g of triphenylphosphine are added at 20 ° C. to a solution containing 0.6 g of the product of preparation 13, 2.24 g of carbon tetrabro ure and 6 cm ³ of methylene chloride. The reaction mixture is kept under stirring for 15 minutes. Poured into water, extracted with methylene chloride, dried and evaporated. 6.2 g of a product are obtained, which product is taken up in a mixture containing 20 cm ³ of chlorine. methylene rure and 10 cm ³ of ethyl ether. The precipitate obtained is filtered and the filtrate is concentrated. 2.1 g of a product are obtained which is chromatographed on silica eluting with a hexane-ethyl acetate mixture (8-2). 0.31 g of sought product is thus obtained, in the form of an oil, δ (CDC1 ₃ ) = 7.78 ppm.

PREPARATION 15: (E) 7- [2- (4-chlorophenyl) ethynyl] o- (metho¬ xymethylene) naphthalene methyl acetate

To a solution of 1 g of the product of preparation 13 and 1 g of bromo 4-chlorobenzene in 10 cm ³ of triethylamine and 6 cm ³ of anhydrous acetonitrile are added 0.15 g of 10% palladium on active carbon, 0.13 g of triphenylphosphine and 0.03 g of cuprous iodide. The resulting suspension is heated to reflux under a nitrogen atmosphere for 2 hours 30 minutes then filtered. The filtrate is diluted with methylene chloride and washed with a 2N aqueous hydrochloric acid solution, dried over MgSO ₄ and then evaporated under reduced pressure. The residue is chromatographed on silica (eluent: CH ₂ Cl ₂ -hexane 7-3) to give 0.75 g of the desired product. F = 162 ^* C.

PREPARATION 16: (E) 7- [2- (4-bromophenyl) ethynyl] α- (methoxymethylene) naphthalene methyl acetate

A 20 cm ^{3 solution} of dimethylformamide containing 1.5 g of product of preparation 13, 1.6 g of iodo 4-bromo-benzene, 0.025 g of dichloro bis (triphenylphosphine) palladium, 0.023 g of cuprous iodide 1.1 cm ³ of triethylamine is stirred at 20 ° C., under a nitrogen atmosphere, for 6 hours then poured into water and extracted with diisopropyl ether. The organic phase is dried over MgSO ₄ and evaporated under reduced pressure. The residue is chromatographed on silica gel (eluent: CH ₂ Cl ₂ -hexane 8-2) to give 2.03 g of sought product. F = 173 "C.

By operating as above, the following products were prepared: PREPARATION 17: (E) α- (methoxymethylene) 7- [3-methyl 3-phenyl 1-butynyl] naphthalene methyl acetate F = 136 ° C. PREPARATION 18: (E) 7- [2- (3-chlorophenyl) ethynyl] α- (metho- xymethylene) naphthalene methyl acetate

F = 194 ^* C.

PREPARATION 19: (E) o- (methoxymethylene) 7- [2- (4-pyridinyl) ethynyl] naphthalene methyl acetate F = 194 ^* C.

PREPARATION 20: (E) α- (methoxymethylene) 7- [2- (4-phenoxypheny1) ethynyl] naphthalene methyl acetate

F = 182 ^* C.

PREPARATION 21: (E) 7- [3- [(2-methoxy) ethoxy] ethoxy 1- propynyl] α- (methoxymethylene) naphthalene methyl acetate

F = 76 ^* C.

PREPARATION 22: (E) 7- [2- (2-chlorophenyl) ethynyl] α- (metho¬ xymethylene) naphthalene methyl acetate

F = 146'C. PREPARATION 23: (E) α- (methoxymethylene) 7- [3-methyl 3- (l- piperidinyl) l-butynyl] naphthalene methyl acetate

F = 145 ^* C.

PREPARATION 24: (E) α- (methoxymethylene) 7- [2- (3-pyridinyl) ethynyl] naphthalene methyl acetate F = 142 "C.

PREPARATION 25: (E) α- (methoxymethylene) 7- [2- (2-pyridinyl) ethynyl] naphthalene methyl acetate

F = 148 ^* C.

PREPARATION 26: (E) α- (methoxymethylene) 7- [3- (4- methylphenoxy) 3-methyl l-butynyl] naphthalene methyl acetate

F <50'C.

PREPARATION 27: (E) α- (methoxymethylene) 7- [3-methyl 3-

(methylpropylamino) l-butynyl] naphthalene methyl acetate F = 128'C.

PREPARATION 28: (E) 7- [3- (4-chlorophenoxy) 3-methyl l-buty¬ nyl] α- (methoxymethylene) naphthalene methyl acetate

F = 114'C.

PREPARATION 29: (E) 7- [2- (3-bromophenyl) ethynyl] a- (methoxymethylene) naphthalene methyl acetate

F = 204'C.

PREPARATION 30: (E) α- (methoxymethylene) 7- [3-methyl 3- (methylamino) l-butynyl] naphthalene methyl acetate F = 152 "C.

PREPARATION 31: (E) 7- [2- [3- (4-fluorophenyl) phenyl] ethynyl] α- (methoxymethylene) naphthalene methyl acetate

F = 164 ^* C. PREPARATION 32: (E) 7- [3,3-dimethyl l-butynyl] o - [[l-

(methyl) ethoxy] methylene] naphthalene methyl acetate

F = 111'C.

PREPARATION 33: (E) α- (ethoxymethylene) 7- [3,3-dimethyl 1-butynyl] naphthalene methyl acetate F = 98 ^* C.

PREPARATION 34: (E) α- (methoxymethylene) 7- [3-methyl 3-

(phenylamino) l-butynyl] naphthalene methyl acetate

F = 154 ^* C.

PREPARATION 35: (E) 7- [3 - [[(2-methoxy) ethoxy] ethoxy] 3- methyl l-butynyl] α- (methoxymethylene) methyl acetate naphthalene

F = 67 ^* C.

PREPARATION 36: (E) 7- [3,3-dimethyl l-butynyl] α- (methoxy¬ methylene) naphthalene 2-trimethylsilyl acetate ethyl F = 105 ^* C.

PREPARATION 37: (E) 7- [2- (4-fluorophenyl) ethynyl] α- (metho¬ xymethylene) naphthalene methyl acetate

F = 170'C.

PREPARATION 38: (E) 7- [2- (4-methoxyρhenyl) ethynyl] α- (methoxymethylene) naphthalene methyl acetate

F = 164'C.

PREPARATION 39: (E) α- (methoxymethylene) 7- [3-

(trimethylsilyl) 1-propynyl] naphthalene methyl acetate

F = 107'C. PREPARATION 40: (E) 7- [3- (4-chlorophenyl) 3-methyl 1- butynyl] α- (methoxymethylene) naphthalene methyl acetate

F = 152 "C.

PREPARATION 41: (E) 7- [2- (3,4-dichlorophenyl) ethynyl] α-

(ethoxymethylene) naphthalene methyl acetate F = 200'C.

PREPARATION 42: (E) 7- [3- (4-chlorophenyl) amino] 3-methyl 1- butynyl] α- (methoxymethylene) naphthalene methyl acetate

F = 149 ^* C. PREPARATION 43: (E) o- (methoxymethylene) 7- [3- [methyl (phenylamino) 3-methyl] l-butynyl] naphthalene methyl acetate

F = 158 ^* C.

PREPARATION 44: (E) 7- [2- [4- (1,1-dimethylethyl) phenyl] ethynyl] o- (methoxymethylene) naphthalene methyl acetate

F = 182 ^* C.

PREPARATION 45: (E) α- (methoxymethylene) 7- [2- (4- methylphenyl) ethynyl] naphthalene methyl acetate

F = 164'C. PREPARATION 46: (E) 7- [2- (4-bromo 2-fluorophenyl) ethynyl] α- (methoxymethylene) naphthalene methyl acetate

F = 135'C.

PREPARATION 47: (E) 7- [2- (3-chloro 4-fluorophenyl) ethynyl] o- (methoxymethylene) naphthalene methyl acetate F = 210'C.

PREPARATION 48: (E) 7- [2- (3,5-dichlorophenyl) ethynyl] α- methoxymethylene) naphthalene methyl acetate

F ≈ 180'C.

PREPARATION 49: (E) α- (methoxymethylene) 7- [2- [4- (trifluoromethoxy) phenyl] ethynyl] naphthalene methyl acetate

F = 150 ^* C.

PREPARATION 50: (E) 7- (3,3-dimethylbutynyl] α-methoxymethylene) naphthalene methyl acetate

F = 138 ^* C. PREPARATION 51: (E) α- (methoxymethylene) 7- [2- [4- (trifluoromethyl) phenyl] ethynyl] naphthalene methyl acetate

F ≈ 157 ^* C.

PREPARATION 52: (E) 7- [2- (3,5-bis (trifluoromethyl) phenyl] ethynyl] α- (methoxymethylene) naphthalene methyl acetate F = 192'C.

PREPARATION 53: (E) 7- [2- (1,3-benzodioxol-5-yl) ethynyl] α-

(methoxymethylene) naphthalene methyl acetate

F = 181'C.

PREPARATION 54: (E) 7- [3- (dimethylamino) 3-methyl l-butynyl] α- (methoxymethylene) naphthalene methyl acetate

F = 148'C.

PREPARATION 55: (E) 7- (1-propynyl) α- (methoxymethylene) naphthalene methyl acetate F = 109 'C.

PREPARATION 56: (E) 7- [3- [(4-chlorophenyl) methylamino] 3- methyl l-butynyl] α- (methoxymethylene) naphthalene methyl acetate F = 179 ^* C.

PREPARATION 57: (E) 7- [2- (4-cyanoρhenyl) ethynyl] α-

(methoxymethylene) naphthalene methyl acetate

F = 129 ^* C.

PREPARATION 58: (E) 7- [2- (2,4-dichlorophenyl) ethynyl] α- (methoxymethylene) naphthalene methyl acetate

F = 156'C.

PREPARATION 59: (E) 7- [2- (2,3-dichlorophenyl) ethynyl] α-

(methoxymethylene) naphthalene methyl acetate

F = 153 ^* C. PREPARATION 60: (E) 7- [2- (2,5-dichlorophenyl) ethynyl] o-

(methoxymethylene) naphthalene methyl acetate

F = 162'C.

PREPARATION 61: (E) 7- [3- (1,1-dimethylethoxy) 3-methyl 1- butynyl] α- (methoxymethylene) naphthalene methyl acetate F = 140 ^* C.

Claims

CLAIMS 1) Use of the compounds of formula (I):

in which R represents:

- a hydrogen or halogen atom,

an alkyl radical containing up to 8 linear, branched or cyclic saturated or unsaturated carbon atoms, optionally substituted by one or more hydroxyl radicals, by one or more halogen atoms, optionally interrupted by one or more heteroatoms chosen from oxygen, nitrogen or sulfur atoms,

- a radical - (CH ₂ ) N ^' ^R '2 in which p represents an integer equal to 0, 1, 2, 3,

4, 5 or 6, and R'- _{j ^} and R ' _2, identical or different, represent a hydrogen atom, a linear or branched alkyl radical, containing up to 4 carbon atoms,

- an aryl or aryloxy radical containing up to 18 carbon atoms optionally substituted on the aryl ring by one or more substituents chosen from halogen atoms, the radical N0 ₂ , the radical C≡N, the alkyl radicals, 0- alkyl and S-alkyl, linear, branched or cyclic, saturated or unsaturated, containing up to 8 carbon atoms, optionally substituted by one or more halogen atoms, aryl or aryloxy radicals containing up to 16 atoms carbon, optionally substituted by one or more halogen atoms and the radical

wherein R '^ and R " ₂ , identical or different from each other, represent a hydrogen atom, an alkyl radical containing up to 4 carbon atoms or an aryl radical containing up to 18 atoms carbon, optionally substituted by one or more halogen atoms,

- an aryl or aryloxy radical containing up to 18 carbon atoms optionally substituted on two adjacent carbon atoms of the aryl ring by a methylene or ethylenedioxy group optionally substituted by one or two halogen atoms, - a heterocyclic aryl radical with 5 or 6 members containing 1, 2 or 3 heteroatoms chosen from oxygen, sulfur and nitrogen atoms, optionally substituted by one or more radicals chosen from the group consisting of hydroxyl radicals, N0 ₂ , C≡N, halogen atoms, alkyl, 0-alkyl and S-alkyl radicals, containing up to 8 carbon atoms, linear, branched or cyclic optionally substituted by one or more halogen atoms, by one or more radicals hydroxyl and radicals

in which R "'- ^ and R'" _{2, which are} identical or different, represent a hydrogen atom or an alkyl radical containing up to 4 carbon atoms,

- a radical

in which Ra, Rb and Rc, identical or different, represent a linear, branched or cyclic alkyl radical containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms, an aryl radical optionally substituted by a or more halogen atoms, one or more hydroxyl radicals, one or more alkyl radicals, linear or branched, optionally substituted by one or more halogen atoms, one or more O-alkyl or S-alkyl radicals containing up to with 8 carbon atoms, optionally substituted by one or several halogen atoms, ab or R represents a radical -CR 'in which a and b, identical or different, represent a hydrogen atom, a halogen atom, a hydroxyl radical, a linear or branched alkyl radical containing up to '' with 6 carbon atoms optionally substituted by one or more halogen atoms or a linear or branched alkoxy radical containing up to 6 carbon atoms, or a and b form together with the carbon atom to which they are linked a cycloalkyl radical containing up to 6 carbon atoms, and R 'represents one of the values indicated above for R, R ₂ and R ₃ identical or different from each other represent a radical alkyl containing up to 8 carbon atoms, linear, branched or cyclic, optionally substituted by one or more halogen atoms, or by a

radical, in which Ra, Rb and Rc have the meanings cations indicated above, for the manufacture of fungicidal compositions.

2) Use of the compounds of formula (I) as defined in claim 1 in which the radical R ₂ represents a methyl radical, for the manufacture of fungicidal compositions.

3) Use of the compounds of formula (I) as defined in claim 1 or 2 in which R ₃ represents a methyl radical, for the manufacture of fungicidal compositions. 4) Use of the compounds of formula (I) as defined in claim 1 to 3 in which the geometry of the exo double bond (enol ether) is E, for the manufacture of fungicidal compositions.

5) Use of the compounds of formula (I) as defined in any one of claims 1 to 4 in which R represents an alkyl radical containing up to 6 carbon atoms, for the manufacture of fungicidal compositions.

6) Use of the compounds of formula (I) as defined in claim 5 in which R represents an isopropyl or terbutyl radical, for the manufacture of fungicidal compositions.

7) Use of the compounds of formula (I) as defined in any one of claims 1 to 4 in which R represents

^a \ - ^b a radical -CR 'in which a and b identical or different represent a hydrogen atom, a hydroxyl or alkoxy radical containing up to 4 carbon atoms, a linear or branched alkyl radical containing up to with 4 carbon atoms or a and b form together with the carbon atom to which they are linked a cycloalkyl radical containing up to 4 carbon atoms and R 'has the meaning indicated in claim 1, for the manufacture of fungicidal compositions.

8) Use of the compounds of formula (I) as defined in claim 7, in which R represents a radical:

C H

for the manufacture of fungicidal compositions.

9) Use of the compounds of formula (I) as defined in claim 7, in which R represents a radical

for the manufacture of fungicidal compositions.

10) Use of the compounds of formula (I) as defined in any one of claims 1 to 4 in which R represents a hydrogen atom, a phenyl radical, a radiethyl trimethyl silyl or a pyridinyl radical, for the manufacture of fungicidal compositions.

11) Use of the compounds of formula (I) whose names follow:,

- (E) 7- (3,3-dimethyl l-butynyl) - (methoxymethylene) l-naph¬ talene methyl acetate

- (E) 7- (3-methoxy 3-methyl l-butynyl) α- (methoxymethylene) l-naphthalene methyl acetate - (E) 7- (3-methyl l-butynyl) - (methoxymethylene) l-naphta¬ methyl acetate

- (E) α- (methoxymethylene) 7- [2- (trimethylsilyl) ethynyl] 1- methyl naphthalene acetate

- (E) 7- [2- [1- (4-ethoxyphenyl) cyclopropyl] ethynyl] α- (methoxymethylene) l-naphthalene methyl acetate

- (E) α- (methoxymethylene) 7- (phenylethynyl) l-naphthalene methyl acetate

- (E) 7- (3-hydroxy 3-phenyl 1-propynyl) α- (methoxymethylene) l-naphthalene methyl acetate - (E) - (methoxymethylene) 7- (ethynyl) l-naphthalene acetate methyl

- (E) α- (methoxymethylene) 7- [2- (3-pyridinyl) ethynyl] naph¬ talene methyl acetate for the manufacture of fungicidal compositions. 12) Use of the compounds of formula (I) as defined in any one of claims 1 to 11 for the manufacture of fungicidal compositions, containing from 0.001 to 1% by weight of compounds of formula (I). 13) Fungicidal compositions containing from 0.0001 to 1% by weight of compounds of formula (I).